Pyrimidyl azo dyestuffs



United States Patent 3,342,798 PYRIMIDYL AZO DYESTUFFS Paul Dussy, St-Louis, France, and Jiirg Ammann, Base], and Werner Bossard, Riehen, near Basel, Switzerland, assignors to J. R. Geigy A.-G., Basel, Switzerland No Drawing. Filed May 22, 1959, Ser. No. 814,997 Claims priority, application Switzerland, May 23, 1958, 59,840, 59,841 15 Claims. (Cl. 260146) The present invention concerns new reactive azo dyestuffs and processes for the production thereof. In addition it concerns processes for the dyeing and printing of fibres or textiles made up therefrom by using these new dyestufls and finally, as industrial product, it concerns the dyed or printed materials themselves.

It has been found that azo dyestuffs which contain at least one trihalogen pyrimidylamino group can be fixed so that they have particularly good fastness to Washing on textile material containing hydroxyl groups and proteins such as, for example, cotton or wool.

The new reactive dyestuffs are produced by reacting sulphonated, possibly cupriferous monoor dis-azo dyestuifs which contain at least one amino group which can be substituted with 2.4.5.6-tetrahalogen pyrimidine wherein the halogen has an atomic weight of at least 35 and not more than 80, the reaction being performed under such conditions that dyestuffs are formed which contain at least one trihalogen pyrimidylamino group.

In the broadest aspect, the dyes of the instant invention correspond to the general Formula I F represents the radical of a sulphonated, cupriferous or nonheavy metal-containing monoor dis-azo dyestulf,

Hal Hal and Hal each represents a halogen atom of an atomic weight of 35 to 80, in particular chlorine, or also bromine,

Py represents a pyrimidyl radical,

R represents hydrogen or lower alkyl, and

n represents a low whole number, advantageously, possibly also 2.

More specifically, the dyes of the instant invention correspond to the general Formula II In this formula:

wherein A represents a radical selected from the group consisting of radicals of the benzene, naphthalene, pyrene, benzthiazole and Z-phenylnaphtho-l.2.3-triazole series,

B represents a radical selected from the group consisting of radicals of the benzene, naphthalene and pyrazole series,

D represents a radical selected from the group consisting of radicals of the benzene and naphthalene series,

Py represents a pyrimidyl radical bound to the NH being bound to vicinal positions with respect to the azo group.

It is difiicult to determine from the dyestutf molecule which halogen atom of the tetrahalogen pyrimidine is exchanged for the dyestulT amino radical. Very probably the latter radical is bound to the pyrimidine ring in the 2- or 4-position. In this case, the halogen atoms are in the 4.5.6- or 2.5.6-positions. The characteristic radical Py-Hal thus has the structure in which Hal has the meaning given above and of X and X one is tertiary nitrogen (=N) and the other is =CHal.

The amino groups which can be substituted in the aminoazo dyestufis used as starting products are advantageously primary amino groups.

It is possible however, also to use dyestulfs having secondary amino groups. The one substituent of secondary amino groups is then advantageously low molecular, i.e. for example, a methyl, ethyl or hydroxyethyl group. Aminoazo dyestuffs which contain negative substituents such as e.g. sulphonic acid or arylazo groups in the 0- position to the amino groups are less suitable starting products in the present process because of the increased difficulty in substituting these amino groups. Aminoazo dyestuffs in which the substitutable amino groups are aromatically bound are preferred to dyestuffs having aliphatically bound amino groups because they are more easily accessible. The amino group can be bound to an aryl radical linked to the azo group direct or it can be in a substituent of this aryl radical, for example, in a benzoylamino group. Either the diazo or also the coupling component, possibly both and, in disazo dyestuffs, also the middle components can contain amino groups which can be substituted.

In the process according to the invention, chiefly technically easily accessible aminoazo dyestuifs are used which are obtained by coupling diazo components with coupling components. At least one of these components however should contain an amino group which can be substituted in the dyestuff molecule or a substituent which can be converted into such an amino group. substituents which can be converted into amino groups in the dyestuff molecule are, for example, the nitro group which is reduced and acylamino groups which are saponified.

mor p-Nitraniline monosulphonic acids and 4- or 5- acylamino-Z-aminobenzene 1 sulphonic acids, also 4- acylamino-4-aminodiphenyl-3'-sulphonic acids, 4 acylamino-3-aminoazobenzene 4' sulphonic acids and 4 acylamino-4'-aminoazobenzene-3-sulphonic acids can be used, for example, as diazo components having substituents which can be converted into substitutable amino groups. Amino-hydroxy-naphthalene compounds, in particular the sulphonic acids which can be coupled in an alkaline medium, also aromatic amines coupling in the p-position to a primary or secondary amino group can be used as coupling components containing amino groups. Some of the more important representatives of these two classes of coupling components containing amino groups are: 2-amino-S-hydroxynaphthalene-7-sulphonic acid, 2- amino-8-hydroxynaphthalene-6-sulphonic acid, l-amino- -hydroxynaphthalene-7-sulphonic acid, l-amino 8 hydroxynaphthalene-4-sulphonic acid, 1-amino-8-hydroxynaphthalene-3.6- or -4.6-disulphonic acid as Well as their rnor p-aminobenzoyl derivatives, 2-mor -p-aminophenyl-(l-hydroxynaphtho-5.6')-thiazole or -imidazoleor -l.2.3-triazole-3-sulphonic acid, 2-mor -p-aminobenzoylamino-6-hydroxynaphthalene-S-sulphonic acid, also aniline and derivatives thereof nonionogenically substituted in the 2- and/ or 5position, in particular the alkyl, alkoxy and acylamino compounds, for example methyl, ethyl, hydroxyethyl, methoxy or ethoxy and acetylamino compounds.

When in the starting compound, both the radical of the diazo component and the coupling component each contain a substitutable amino group, then reactive dyestuffs according to the invention having two trihalogen pyrimidylamino radicals are obtained. However, also dyestuffs having more than two such reactive radicals are also within the scope of the invention. Preferred dyestuffs according to the invention however only contain one single trihalogen pyrimidylamino group. For this reason, aminoazo dyestufls with one single substitutable amino group are the preferred starting compounds.

The starting compounds can contain other substituents usual in azo dyestuffs. They should contain at least one sulphonic acid group; advantageously the end dyestuffs contain two to three such groups. Instead of further sulphonic acid groups, also other acid dissociating, water solubilising groups can be present, such as e.g., carboxyl groups or acylated sulphonic acid amide groups.

Finally, aminoazo dyestuffs used according to the invention can also contain copper bound in complex linkage. In this case they are advantageously the complex copper compounds obtained by known methods from o.o-dihydroxy or o-hydroxy-o'-carboxy-aminoazo dyestuffs by treatment with agents giving off copper.

The aminoazo dyestuiis are reacted with a tetrahalogen pyrimidine advantageously in the form of the aqueous solutions of their alkali salts. The reaction is performed advantageously at room temperature; sometimes gentle heating to about 40-60 is necessary. The acid formed during the reaction is advantageously buffered or neutralised. Sodium acetate, sodium carbonate, caustic soda lye, pyridine, dior tri-sodium phosphate or, possibly, mixtures of butfer salts are used as mineral acid binding agents. The reaciton conditions are always so chosen that only one halogen atom of the pyrimidine compound is exchanged. Mild conditions are also indicated in the isolation and drying of the dyestuffs according to the invention in order to prevent the premature exchange of other halogen atoms. Chiefiy the easily accessible 2.4.5.fi-tetrachloropyrimidine is used as tetrahalogen pyrimidine. As bromine derivative, e.g. the 2.4.6-trichloro- S-bromopyrimidine is used which is obtained, for example from 5-bromobarbituric acid and POCI in the presence of a tertiary base. The halogen atom in the 5-position increases the reactivity of the other halogen atoms in the pyrimidine radical. Often it is possible, often it is even indicated, to produce the reactive dyestufis according to the invention by a somewhat modified process. This consists in building up the dyestuffs from diazo components and coupling components which together contain at least one trihalogen pyrimidylamino substituent. In this case also, the components must be so chosen that the dyestuffs have at least one sulphonic acid group.

Examples of such diazo components are the 4- or S-trihalogen pyrimidylamino 2 aminobenzene-l-sulphonic acids, the 4-trihalogen pyrimidylamino-1-aminonaphthalene-6- or -7-sulphonic acids, 4- or 5-(4- or 3'-trihalogen pyrimidylamino-benzoylamino) 2 aminobenZene-l-sulphonic acids.

Examples of azo components used according to the modified process having a trihalogen pyrimidylamino group as defined are obtained from the coupling components listed above which can be coupled in an alkaline medium and contain amino groups, if they are reacted with a tetrahalogen pyrimidine before being used for coupling. They can be coupled with any diazo compounds, in particular also with diazobenzene sulphonic acids desired.

A valuable class of dyestuffs according to the invention correspond to the general Formula III Y (III) wherein A represents a member selected from the group consisting of sulphonated aromatic radicals of the henzene, naphthalene, pyrene, benzthiazole and 2-phenylnaphtho-1.2.3-triazole series,

B represents an aromatic radical containing at least one six-membered carbocyclic nucleus and at most two such nuclei condensed with one another,

Py represents a pyrimidyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 halogen atoms in the o-position and l halogen atom in the m-position to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80,

X represents a member selected from the group consisting of hydrogen, alkyl and alkoxy groups,

Y represents a member selected from the group consisting of hydrogen, alkyl, alkoxy and acylamino groups, and

n represents a whole positive number of at most 2.

Particularly valuable dyestufis are obtained if A is the radical of a naphthalene disulphonic acid.

A further class of valuable dyestufis according to the invention corresponds to the general Formula W wherein A represents a radical selected from the group consisting of radicals of the benzene and naphthalene series,

B represents a radical selected from the group consisting of radicals of the naphthalene and pyrazole series,

Py represents a pyrimidyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 halogen atoms in the o-position and 1 halogen atom in the m-position to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80,

Z represents a member selected from the group consisting of OH and NH bound in o-position to the azo group,

p represents a Whole positive number of at most 2, and

q represents a whole positive number of at most 4.

Within this class, an important sub-class consists of the coupling products of o-diazobenzene sulphonic acids and l-hydroxy-naphthalene-S'-sulphonic acids which contain an amino group in the 5-, 6-, 7- or 8-position and, posslbly, further sulphonic acid groups.

A first group of preferred dyes therefore corresponds to the general Formula V.

In this formula:

, S represents hydrogen or a substituent selected from the group consisting of halogen, sulphonic acid, lower alkyl, lower fatty acid acyl amino, benzoylamino and Hal groups S represents hydrogen or a sulphonic acid group,

n represents 1 and 2,

one of X and X represents a tertiary nitrogen (=N), and the other of X and X represents =CHal, and

Hal represents a halogen atom of an atomic weight of at least 35 and at most 80, preferably chlorine.

In this formula, the amino substituent of the naphthalene radical is preferably situated either in the 6-position (counting HO/SO H as 1.3) and S is then preferably hydrogen, or in the 8-position and S is then preferably -SO H in the 5- or preferably in the 6-position. -If the pyrimidyl radical is not directly connected with the NH substituent of the naphthalene nucleus, then S is preferably SO H.

A further sub-class of valuable dyestuffs consists of the coupling products of trihalogen pyrimidylarnino-Z-diazobenzene-l-sulphonic acids and acylated l-hydroxy-5-, -6-, -7- or -8-aminonaphthalene-3-sulphonic acids in which the acyl radical, for example the acetyl radical, the chloracetyl radical, the p-chloroor fl-bromo propionyl radical, the benzoyl radical, an acylaminobe'nzoyl radical,

the p-toluene sulphonyl radical and the naphthalene radi- 50 cal, can be further sulphonated.

A second group of preferred dyes therefore corresponds to the general Formula VI 1 In this formula, Hal, X and X have the same meanings as given in Formula V, S is hydrogen or SO H and R is 6 hydrogen or a lower fatty acid acyl or benzoyl.

Also in these dyes, the amino substituent of the naphthalene radical is preferably either in the 6-position (counting H-O/SO H as 1.3) and S is then hydrogen, or

it is in the 8-position and S is then preferably SO H inthe 6-position.

' A further valuable class of dyestuffs according to the invention consists of the coupling products of o-diazobenzene sulphonic acids and S-hydroxyor S-aminopyrazoles. In these products,,the amino group which is 7 6 either substituted or to be substituted is advantageously in the diazo component.

A third group of preferred dyes therefore corresponds to the general Formula VII SO H Also in this formula, Hal, X and X have the same meanings as given in Formula V, Y is oxygen or NH,

R is hydrogen or a radical of the benzene or naphthalene series and R is a lower aliphatic radical and preferably CH A last class of valuable azo dyestuffs according to the invention are the complex copper compounds of o.o-dihydroxyand o-hydroxy-d-carboxy azo dyestulfs corresponding to the general Formula VIII J NH (VIII) wherein A represents a radical selected from the group consistof radicals of the benzene or naphthalene series,

B represents a radical of the naphthalene series,

Py represents a pyn'midyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 halogen atoms in the o-position and l halogen atom in the m-position to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80,

k represents a whole positive number of at most 2,

and

q represents a whole positive number of at most 4, the group (CO) OCuO being bound to vicinal positions with respect to the azo group.

These compounds are advantageously the derivatives of coupling products of o-hydroxyaminobenzene compounds and the hydroxyaminonaphthalene sulphonic acids mentioned above.

NH-R

S (VI) A fourth group of preferred dyes therefore corresponds to the general Formula IX.

Nil- CO- Hal Mia; 1] Hal In this formula A represents a radical of the benzene series,

Hal, X X and S have the same meanings as indicated under Formula VI, and

k and 11 each means 1 and 2.

In these compounds also, the amino substituent of the naphthalene radical is preferably in the 6-position (counting HO/SO H as 1.3) if S is hydrogen, and it is in the 8-position if S is a SO H group either in the 5- or, preferably, in the 6-position.

Of all these preferred end products, finally the ones of particular importance are those which contain at least two to three sulphonic acid groups.

In the form of their ammonium or alkali metal salts, the reactive dyestuffs produced according to the present processes are powders which are soluble in hot water. The new dyestuffs are suitable for the dyeing and printing of fibrous material containing hydroxyl groups or protein, in particular of cotton, in yellow, orange, red, violet, blue, brown to black shades. Cellulose material is impregnated advantageously at a low temperature, for example 2050, with the dyestuff solution and the dyestuff is then fixed by a treatment with acid binding agents; as such are used, for example, sodium carbonate, caustic soda lye, diand tri-sodium phosphate and, at over 50, also sodium bicarbonate. Although this treatment can be performed with these agents even at a slightly raised temperature, it is often performed, advantageously after an intermediate drying of the goods, with better results at temperatures of from, for example, 60-160". Instead of this alkaline aftertreatment of the impregnated goods, the goods can also be treated before or during the impregnation process with the acid binding agents. By this treat ment with agents having an alkaline reaction, after soaping, cellulose dyeings are obtained which have excellent wet fastness properties, in particular first-rate fastness to boiling.

For the dyeing of protein fibrous material, the new dyestuffs are used advantageously in a weakly acid, for example a weakly acetic acid, bath. Often the addition of compounds containing basic nitrogen, for example of polyquaternary ammonium compounds, and/ or of nonionogenic distributing agents having the properties of protective colloids, is necessary or indicated. If necessary, the dyeing is then given an after treatment with mineral acid binding agents such as e.g. ammonia or hexamethylene tetramine.

Example 1 67.2 parts of the amino monoazo dyestuif of the formula are dissolved in 1200 parts of water and caustic soda lye is added so that the pH value of the solution is 6.5-7.0. 26.2 parts of 2.4.5.6-tetrachloropyrimidine, dissolved in 100 parts of acetone and an aqueous solution of sodium carbonate are added dropwise simultaneously within 1 hour at 3035 in such a way that the reaction always remains neutral. As soon as the condensation is com pleted, the dyestuif of the formula lea-R in which R represents the 4.5.6-trichloropyrimidyl-(2) or the 2.5.6-trichloropyrimidyl-(4) radical, is precipitated by the addition of sodium chloride. It is filtered off, washed with diluted sodium chloride solution and dried carefully in the vacuum. It is a dark powder which dissolves in water with a red colour.

Cotton is treated at in the foulard with a 1% solution of this dyestuff which contains also 20 parts of sodium carbonate and 200 parts of urea per litre. The impregnated goods are dried, then heated for 4 minutes at 140-160 and finally soaped at the boil for 30 minutes. An even red dyeing is obtained which is fast to boiling in water.

Dyestuffs with similar properties are obtained if, instead of the amino monoazo dyestuff mentioned above, corresponding number of parts of the dyestuffs named in the following Table I are used and these dyestuffs are condensed under the same conditions with the corresponding number of parts of the halogen pyrimidine compounds given in the table.

TABLE I No. Amino azo dyestuffs Condensing agents Shade on cotton 1 l-aminobenzene-Z.5-disulph0nio acid 2-(3-amino- 2.4.5.6-tetrachloropyrim- Orange.

benzoylamino)-5-hydroxynaphthalene-7-sulphonic acid. idine.

2 1-am1n0benzene-2.5-disulphonic acid 1-(3-aminodo Red.

benlzoylammo)-8-hydroxynaphthalene-3.G-disulphonic aci 3 2-a1nin0naphthalene-6.8-disulphonic acid 2-(4- 5-bromo-2.4.6trichloro- Red.

annnobenzoy lamano)-5-hydroxynaphthalene-7- pyrimidine. sulphonic acid.

4 l-annnobenzene-Z-sulphonie acid 1-(3-amino- 2.4.5.6tetrachloropyrimi- Red.

bertiizoylammo)-8-hydroxynaphthalene-3.6-disulph0nic dine. aci

5 1-aminobenzene-2.4-disulphonic acid 1-(3-aminodo Red.

benizoylammo)-8-hydroxynaphthalene-3.6-disulphonic ac] 6 l-aminobenzene-ZA-disulphonic acid 2-(3-an1inodo Orange.

benizoylammo)-5-hydroXynaphtha1ene-7-sulphonic aci The following examples serve to illustrate the inven- Example 2 tion without limiting it in anyway. In these examples, as well as in the foregoing, the temperatures are in degrees centigrade. Parts are given as parts by weight and their relationship to parts by volume is as that of grammes to cubic centimetres.

31.9 parts of 1-amino-8-hydroxynaphthalene-3.6-disulsolved in 100 parts of acetone, are added dropwise within 1 hour-and the pH value of the reaction mixture is kept at 6.06.5 by the gradual addition of ,caustic soda lye. After stirring for 1 hour, no more diazotisable amino 1 neutral with sodium carbonate. 26.2 parts of 2.4.5.6-tetrachloropyrimidine, dissolved in 100 parts of acetone, are then added dropwise at 20-25 simultaneously with an aqueous trisodium phosphate solution so that the reaction groups can be traced. The reaction product is precipitated mixture always remains neutral. As soon as the reaction with sod1um chloride, filtered off and dissolved at 25 is complete, the reaction product is precipitated by the In 300 parts of water. 30 parts of sodium bicarbonate are addition of sodium chloride, filtered off, dissolved in 300 added to this solution and then the solution of 13.7 parts parts of water and the solution is diazotised at 0 with of drazotised 1-ammobenzene-2-carboxylic acid is poured parts of hydrochloric acid and 6.9 parts of sodi- 1n W1th1n 30 mlnutes. As soon as the coupling is com- 1 um nitrite. The diazonium compound formed is poured pleted, 207 by volume of sodium chlorlde and sufiicient into a solution of 20.4 parts of 1-phenyl-pyrazolone-(5)- hydrochloric acid are added so that the new dyestuif of carboxylic acid-(3) in 200 parts of water and 34.0 parts the formula of sodium bicarbonate. On completion of the coupling,

OH 1 i the new dyestufi" of the formula D 11038 soiH 0 u n I wherein R is the 4.5.6-tr1ch1oropyrim1dyl-(2) or the 2.5.6- 20 OH hl 1 4 V 1 d RNH SO3H tric oropyr1m1 y ra ica preclpitates. It is filtere off and dried in a vacuum at -45. It is a dark red powder which dissolves in water with a red colour. Whefelh R is the -t py y or the On treating cotton with a 1% solution of this dyestuff PY Y radical, is Precipitated With 1n the foulard, drying, then treating with a l ti 25 sodium chloride. It is filtered off and dried in the vacuum taining 2% caustic soda lye and 30% sodium chloride, at It is a yellow POWdsI Which dissolves n fixing for 4 minutes at 140-160, rinsing and soaping for ter with a yellow colour. 30 minutes at the boil, then a brilliant red dyeing is .ob- It Cotton iS treated n the f rd at 20 With a 1% taincd which is fast to water boiling. aqueous solution of this dyestuif, dried, then treated with If in the above exam le in tead of the conden ation 30 a 2% sodium carbonate solution which also contains 30% Produ t produced from l-amino-8-hydroxynaphthalenesodium chloride, then steamed for 5 minutes at 100-103", 3.6-disulphonic acid and 2.4.5.6-tetrachloropyrimidine as then rinsed and finally S p at the boil for 30 minutes, acylation agent, the corresponding number of parts of then a yellow dyeing which is fast to boiling is obtained. the coupling components named in the following Table Dyes uffs hav ng Similar PI PeItieS are Obtained if in- II and of the acylation agents are used and, instead of 35 stead of the diazo component obtained by condensation of 1-aminobenzene-2-carboxylic acid, the corresponding 1.3-diaminobenzene-4-sulphonic acid with 2.4.5.6-tetranumber of parts of the following diazo components are chloropyrimidine as acylating agent, the corresponding used, then dyestuffs having similar properties are obnumber of parts of the diazo components and acylating tained. agents given in the following Table 111 are used and, in-

TABLE II No. Diazonium compound from Coupling component Acylating agent Shad): on

1. 1-amino-4-acety1amin0benzene-2- l-arnino-8-hydroxynaphthalene-3.fi-di- 2.4.5.6-tetrach1oropyrimidine.. Red violet.

sulphonic acid. sulphonic acid. 2 1-amino-3-acety1arnin0benzene-4 .-...do ..do Blueish red.

sulphonic acid. 3... l-aminobenzene-2.5-d.isulphonic acid 2-amino-8-hydroxynaphthalene-6- ...d0 Red-orange.

sulphonic acid. 4 1-amino-3-acetylaminobenzene-fi- .-...do 5-bromo-2.4.fi-trichloropymmdme..- Scarlet.

sulphonic acid. 5.... 4-(3-methyl-4aminobenzoylamino)-1- Z-amino-5-hydroxynaphtha1ene-7- 2.4.5.6-tetrach1oropynm1d1ne Red.

hydroxybenzene-zcarboxylic acid-d sulphonic acid. sulphonic acid. 6-.... l-aminoi-acetylaminobenzene-Zi-carbox- .-...dn .-..dn

ylic acid. 7 1-amino-4-acety1aminobenzene-2-carbox- .....do ..do.....

xylic acid. 8-.... l-aminobeuzene-Z-sulphonic acid l-amino-8-hydroxy11aphthaleue-3.6-di ....do

sulphonic acid. 9-.... l-aminobenzene-Z-carboxylic acid-4- 2-amino-5-hydroxynaphthalene-7- .....do

sulphonic acid. sulphonic acid. 10.-.. l-amino-t-acetylaminobenzene-2- .-...do 5-br0n1o-2.4.(i-tnchloropymmdme--. Scarlet sulphonic acid. 11.... 2-aminonaphthalone-4.8-disulphonic acid.- .-...do 2.4.5.6-tetrachloropyr1m1d1ne Red. 12.-.. l-aminobenzene-2.5-disulphonic acid.-.--. 2-(3-aminobenzoylamino)-5-hydroxy. ..do Do.

naphthalene-7-sulphonic acid. 13-.-. 1-amin0-4-acetylaminobenzene-2- 1-amino-8-hydroxynaphthalene-4.6-di- ..-..do Ruby red.

sulphonic acid. sulphonic acid. 14.... l-amino-B-acetylaminobenzene-d 1-amino-5-hydroxynaphtha1ene-7- Orange.

sulphonic acid. sulphonic acid. 15.... .....do l-amino-B-hydroxynaphtha1ene-3.fi-di- Red.

sulphonic acid. 16.-.. 1-amino-3-benzoylaminobenzene-fi- 1-amino-8Fhydr0xynaphthalene-3.6-d1- 2.4.5.6-tetrach1or0pynm1d1ne Do.

sulphouic acid. sulphonic acid. 17.... 1-amino-3-acety1am nobenzene6- 2-amino-5-hydroxynaphthalene-7- .....do Orange.

sulphonic acid. sulphonic acid. 18-... 1-amino4-methy1benzene-(i-sulphonic acid. 1-am1i111 1)-8- hydrgxynaphthaleue-3fi-d1- .-...d0 Bluelsh red.

511 p omc aci 19.... 1-amino-4-chlorobenzene-6-sulphonic acid. .do ..do Do. 20...- o do 5-bromo-2.4.fi-tnchloropynmrdrne..-. Do. 21.... 1-amino-4-methy1benzene-6-sulphonic mino-5-hydr0xynaphthaleue-7- ..--do Orange.

acid. sulphonic acid. 22-... .-oo do 2.4.5.6-tetrachloropyr1midine Do.

Example 3 18.8 parts of 1.3-diaminobenzene-4-sulphonic acid are dissolved in 200 parts of water and the reaction is made stead of l-phenyl-pyrazolone-(S)carboxylic-S-acid, the corresponding number of partsof the coupling components given in the same table are used.

TAB LE III No. Diazonium compound Acylating agent Qoupling component Shade on cotton 1..... 1.4-diaminobenzene-3-sulphonic acid- 2.4.5.G-tetrachloropyrimidine Z-acetyfiamino-fihydroxynaphthalene-7- Scarlet.

su p 01110 aci 2. 1.3-diaminobenzene-4-sulphonic acid. .....do 1-(2-ehlo?0-5-sulphophenyl-3-mothyl-5- Greenish yellow.

pyrazo one. 3 do do l-naphthyl-(2)-3-methyl-5-pyrazolonc- Lemon yellow.

4.8-disulphonic acid. 4..... ...-.do 5-bromo-2.4.6-triohloropyrimidine--... l-benzoylamino-B-hydroxynaphthalene- Blueish red.

3.6-disulphonic acid. 5 ..do dol-acetylamino-S-hydroxynaphthalene- Red.

3.6-disulphonic acid. 6 ..do 2.4.5.S-tetrachloropyrimidine 1-pl11enyl-3-m1ethy1-5-pyrazolone-3'-sul- Yellow.

p ionic aci 7 do do 2-amino-hydroxybenzcneA-sulphonic Brown.

u acid 1.3-dihydroxybenzene. 8 ..do 5-bromo-2.4.B-trichloropyrimidine l-phienyl-3qnfthyl-fipyrazolone-ii-sul- Yellow.

p onic aci 9. 1.4-diaminobenzene-B-sulphonic acid- 2.4.5.G-tetrachloropyrimidine Z-acetyfiamino-tfihydroxynaphthalene-6- Red.

su p onic acl 10.... ..-..do do. 1-4-sulphophenyl)-3-methyl-5-pyrazo- Yellow.

one. 11.... 1.3-diaminobenzene-4sulphonie acid. ..-..do l-naphthyl-(2)-3-methyl-5-pyrazolone- Do.

6.7-disulphonie acid. 12.... 1.4-diaminobenzene-3-sulphonic acid. 2.4.5.6-tetrachloropyr1m1dme 3-mcthyl-5-pyrazolono Do. 13.... ...-.do ..do 1-benzoylamino-fi-hydroxynaphthalenc- Red.

7-sulphonic acid. 14.... 1.3-dian1inobenzene-4'sulphonic acid. ....do 1-acety1amino-8-hydroxynaphthalene- Do.

8.6-disulphonic acid. 15.... 4.4-diaminodipl1enyl-3-sulphonic acid. .....do o- Violet. 16--. 1.4-diaminobenzene-3-sulphonic acid- 5-bromo-2.4.6-tetrachloropyr 2-aceltyilamino- 5hydroxynaphtlialene-7- Orange.

su p onic aci 17. do 5-bromo-2.4.G-trichloropyrimidine. l-acotylamino-8-hydroxynaphthalene- Red violet.

3.6-disulphonie acid. 18.... 1.3-dia1ninobenzene4-sulphonic acid- 2.4.5.6-tetrachloropyr1midine.. l-benzoylamino-8-hydroxynaphthalene- Blueish red.

3.6-disulphonic acid. 19. 1-(4-aminobenzoylamino)-3-amino- 1-acetylamino-S-hydroxynaphthalene- Do.

benzenei-sulphonic acid. 3.6disulphonic acid. 20. ..do 1-(2.5-disulphophenyl)-3-methyl-5- Greenish yellow.

pyrazolone. 21.... 1.B-diaminobenzene-ei-sulplionic acid- 1-(3-sulp1l1ophenyl)-3-methyl-5-imino- Yellow.

pyrazo e. 22.-.. .....do do. D0. 23.... .....do 1-(4'-sulphophenyl)-3-methyl-5-imino- Do.

pyrazole. 24.-.. .-...do ..do Do.

Example 4 56.5 parts of the amino monoazo duestuff of the formula 1V0: 0 ouo SOQH HOaS NH2 wherein R is the 4.5.6-trichloropyrimidyl-(2) or the 2.5.6- trichloropyrimidyl-(4) radical, is precipitated by the addition of sodium chloride. It is filtered off and dried in a vacuum at 4045. The dark red powder dissolves in water with a ruby red colour.

2 parts of the dyestuif are dissolved in 4000 parts of water, and 20 parts of caustic soda lye of 36 B are added. parts of cotton are entered at 40-45 and the bath is heated Within 30 minutes to 80-85 and at the same time sodium chloride is added so that finally the content is g. per litre. Dyeing is performed at the boil for 1 hour at this temperature. The goods are then rinsed and soaped for 30 minutes at the boil. The soaping solution is only coloured a little. A level ruby red dyeing is obtained which is fast to light, water and water boiling.

Dyestuffs having similar properties are obtained if instead of the amino azo dyes-tuff given above, the corresponding number of parts of the complex copper compound of the amino azo dyestuffs given in the following Table IV are used and the complex copper compounds are condensed under the same reaction conditions with the corresponding number of parts of the halogen pyrimidine compounds given in the same table.

TABLE IV No. Amino azo dyestufis Condensing agents Shade on cotton 1 Z-aminobenzene-l-carboxylic aeid-4-sulphonic aeid 2-(4-amino- 2.4.5.6-tetrachloropyrimidine Scarlet.

. benzoylamino)-5-hydroxynaphthalene-7-sulphonic acid. 2 2-amino-6 chloro-l-hydroxybenzene-4-sulphonic acid 2-amino-5- 5Jerome-2.4.fi-triehloropyrimidine Bordeaux.

hydroxynaphthalene-7-sulphonic acid. 3 2-amino-l-hydroxybe11zene-4.6-disulphonic acid 2-amino-5- 2.4.5.6-tetrachloropyri.m.idine Ruby.

l1ydroxynaphthalene-7-sulpl1onic acid. 4 Zamino-l-hydroxybenzene-t-methyl sulphone 1-amino-8- 2.4.5.fi-tetraohloropyrimidine Violet.

hydroxynaphthalene-3.fi-disulphonic acid. 5 Z-amino-l-hydroxybenzene-4.G-disulphonic aeid 2-anu'no-5- 5-bromo-2.4.6-trichloropyrimidine Ruby.

hydroxynaplithalene-7-sulpl1onic acid.

TABLE IV-'C0ntinued N 0. Amino azo dyestufis Condensing agents Shade on cotton 6 zamino-hhydroxybenzene-et'sulphonic acid 1.3-dihydroxy- 2.4.5.fi-tetrachloropyrimidine Brown.

benzene l-amine i-acetylaminobenzene-2-sulphonic acid saponified.

7, l. 1-aminobenzene-2.5-disulphonic acid 1-amino-2.5-dimethoxydo Blue.

benzene Z-annnoethylamino-5-hydroxynaphthalene-7- sulphonic acid.

8 4-amino-4-[3-metho1-5'-oxo-pyraz0liny-1-(l)]-stilbene3.3- do Yellow.

disulphonic acid l-aminobenzenezcarboxylic acid-4- sulphonic acid.

9 6-nitro-1-diazo-2-hydroxynaphthalene4-sulphonic acid 2-amiuodo Violet.

5-hydroxynaphthalene-7-sulphonic acid. I

10 2-amino-l-hydroxybenzeneA-methyl sulphone l-amino-S- 5-bromo-2.4.fi-tnchloropyrimidine Do.

hydroxynaphthaleneB.fi-disulphonic acid.

11 Z-amino-l-hydroxybenzene-4.6-disulphonic acid 2-(3-amino- 2.4.5.fi-tetrachloropyrimidine Ruby.

benzoylamino)-5-hydroxynaphthalene-7-sulphonic acid.

12 do 5-bron1o-2.4.fi-trichloropyrimidine Do.

13 2-amino-1-hydroxybenzene-4.6-disulphonic acid 2- in do Do.

benzoylamino)-5-hydroxynaphthalene7-sulphonic acid.

14 do 2.4.5.6-tetrach1oropyrimidine Do.

15 Z-aminobenzene-l-earboxylic acid-4-sulphonic aci 2-(3-aminodo Scarlet.

benzoylamino)-5-hyd.roxynaphthalene7-sulphonic acid.

16 4-amino-4-[3-methy1-5"-oxopyrazolinyl-(l)]-stilbene3.3-disul- 2.4.5.6-tetrachloropyrimidine Yellow.

phonic acid l-aminobenzene-Z-carboxylic acid-fi-sulphonic acid.

17 .-do 5-bromo-2.4.6-trichloropyrimidine Do.

18 l-arm'no-2-hydroxybenzene-4.6-disulphonic acid 1-(3-ami.no- 2.4i5.tS-tetrachloropyrimidine Yellow-brown.

phenyD-EI-methyl-(5)-pyraz0lone.

l9 ..do 5-bron10-2.4.G-trichloropynmidine Do.

20 l-amino-Z-hydroxybenzene-4.6-disulphonic acid 1-(4-aminodo Brown.

phenyl)-3-methyl-(5)-pyrazolone.

21 ..do 2.4.fidtetrachloropynmidine Do.

22 1-aminobenzene-2-carboxylic acid-4-su1phonic acid 1-(3- do Yellow.

aminophenyl)-3-methyl-(5)-pyrazolone.

23 ..do 5-brorno-2.4.G-trichloropyrimidine Do.

24 1-aminobenzene2-carboxylic acid 5-sulphonic acid 1-(4- ...do Yellow-brown.

aminophenyD-3-methyl-(5)-pyrazolone.

25 .-do 2.4.5.6-tetrachloropyrin1idine Do.

Example 5 40.7 parts of the amino monazo dyestuif are dissolved in 500 parts of water with a neutral reaction by means of sodium carbonate. 26.3 parts of 2.4.5.6-tetrachloropyrimidine, dissolved in 100 parts of acetone, and, at the same time, an aqueous sodium carbonate solution are added dropwise to this solution '-35 within one hour in such a manner that the reaction mixture always has a neutral reaction, As soon as no more free amino SI 0 H wherein R is the 4.5.6-trichloropyrimidyl-(2) or the 2.5.6- trichloropyrirnidyl-(4) radical, is precipitated with sodium chloride. It is filtered off and washed with diluted sodium chloride solution. It is a yellow powder which dissolves in water with a yellow colour. If cotton is impregnated with a 1% solution of this dyestuif in the foulard, dried, then treated with a solution containing 2% sodium bicarbonate and 30% sodium chloride, then heated for 4 minutes at 140160, then rinsed and soaped at the boil for 30 minutes, it is dyed yellow and the dyeing is fast to boiling.

If, instead of the 40.7 parts of the above dyestuif, the corresponding number of parts of the dyestuffs given in the following table are used and the dyestufi is condensed with one of the halogen pyrimidine compounds given, then when the above dyeing procedure is followed, dyestuffs are obtained which produce similarly wet-fast groups can be traced, the dyestufi of the formula cellulose dyeings.

TABLE V N 0. Amino monoazo dyestufi Condensing agent Shade on cotton 1 z-abminonaphthalene4.8-disu1phonic acid l-amino-Z-methoxy-fi-methyl- 2.4.5.fi-tetrachloropyrimidine Yellow.

enzene. 2-aminonaphthalene-4.8-disulphonic acid l-amino-3-methylbenzene Do. 1-aminonaphthalene-3.G-disulphonic acid 1-a'mino-3-methy1benzene D0. 1-aminonaphthalene-3.6-disulph0nic acid 1-amino-3-acetylaminobenzene- D0. 2-arninonaphthalene-3.G-disulphonic acid 1-amino-2-ethoxybenzene. Do. 2aminonaphthalene-3.6-disu1ph0nic acid l-amino-B-methylbenzena D0. Z-aminonaphthalene-6.8 di sulph0nic acid lamino-3-methylbenzene Do. 2ami nonaphthalene-4.8-disulphonic acid 1-amino-2.-methylbenzene. Do. 2-ammonaphthalene-fi.8-disulphonic acid 1'amino-3-acetylaminobenzene Do. zaominonaphthalene-6.8-disulphonic acid l-amino-2-methoxy-5-methyl- Do.

61128118. Z-aminonaphthalene-fi.7-disulphonic acid 1-amino-3-ethoxybenzene Do. 2-aliaminonaphthalene-5.7-disulphonic acid l-amin0-3-carbomethoxyamino- Do.

enzene. 13 2-anminonaphthalene-4.8-disu1phonic acid 1-amin0-2-methoxy-5-methyl- Do.

enzene. 14 2aminonaphthalene-3.6.8-trisu1phonic acid 1-amino-3-methylbenzene. D0. ,.15 l-annnonaphthalene-tl.6.8-trisulphonic acid 1amino-3-methylbenzene- Do.

Example 6 30.7 parts of the amino monoazo dyestuff of the formula SOaH are dissolved in 1500 parts of water with a neutral reaction with the aid of sodium bicarbonate. 26.2 parts ture is always about 7.0. On completion of the reaction,

the dyestuff of the formula OCHa SOaH wherein R is the 4.5.6-trichloropyrimidyl-(2) or the 2.5 .6- trichloropyrimidyl-(4) radical, is precipitated by the addition of sodium chloride. It is filtered off and dried. The dyestufr" is a yellow powder which dissolves in water with a yellow colour.

2 parts of the dyestuff are dissolved in 4000 parts of water and parts of caustic soda lye of 36 B are added. 100 parts of cotton are entered at 4045 and the bath is heated within minutes to 80-85. At the same time sodium chloride is added so that finally the content is 150 g. per litre. Dyeing is performed for 1 hour at this temperature. The goods are then rinsed and soaped at the boil for 30 minutes. The soaping solution is only coloured a little. A level, clear yellow dyeing is obtained which is fast to light, washing and water boiling.

Similar dyestuffs are obtained by using compounds given in the following table when the corresponding number of parts are used as described above.

16 Example 7 56.2 parts of the aminodisazo dyestufi S|O3H 0 CH 8 0 11 I IHOOCH CH3 are dissolved in 1500 parts of water with a neutral reaction with the aid of sodium carbonate. 26.2 parts of 2.4.5. 6-tetrachloropyrirnidine dissolved in 100 parts of acetone and an aqueous solution of disodium phosphate are so added dropwise simultaneously to this solution within 1 hour at 30-35" that the reaction mixture always has a neutral reaction. As soon as no more free amino groups can be traced the dyestuff of the formula wherein R represents the 4.5.6-trichloropyrimidyl-(2) or the 2.5 .6-trichloropyrimidyl-(4) radical, is precipitated by the addition of sodium chloride. It is filtered off, washed with a diluted sodium chloride solution and dried in a vacuum at -45". The dyestuff is an orange coloured powder which dissolves in water with a yellow-orange colour.

If cotton is impregnated with a 1% solution of this dyestuff with the addition of 20 parts of sodium carbonate per litre at in the foulard, rolled out, heated for 2 hours at rinsed and then soaped at the boil for 30 minutes, then yellow orange dyeings are obtained which are fast to boiling.

Similar dyestuffs are obtained on using corresponding parts of the compounds given in the following table in the manner described above.

TABLE VI No. Amino monoazo dyestufi amino-2-methoxybenzene.

l-aminobenzene-Z.5-disulphonic acid -v 1-amin0-3-acetylaminobenzene.

l-aminobenzene-2.4-disulphonic acid l-amino-Kcarbethoxyaminobenzene.

l-aminobenzene-2.5-disulphonic acid l-amino-2-methoxy-5- mcthylbenzene.

l-aminobenzene-zcarboxylic acid-i-sulphonic acid Lamina-3- acetylaminobenzenc. l-aliaminobenzene-zcarboxylic acid-5-sulphonic acid l-arninoenzene. l-aminobenzene-Z-carboxylic acid-4-sulphonic acid 1-amino-3- methylbenzene.

methoxy-fi-methylbenzene.

aminohenzene. l-aminohenzene-2.5-disulphonic acid 1-arnino-2-methoXy-5- methylbenzene.

1-amino-3-carbomethoxyaminobenzene. 6-methyl-2-(3-sulpho-4-aminopheny1)-benzthiazole sulphonic acid-(7) l-amino-S-methylbenzene. 2- (4-aminophenyl) -[naphtho-1' .2 :4.51-1.2.3-triazole-2".6'-disulphonic acid l-aminobenzene phonic acid 1-amino-3-methylbenzene. mixture from 3-aminopyrene-5.8-disulphonic acid and 3-aminopyrene-5.10-disulphonic acid 1-arnino-3-rnethyl benzene. mixture from 3-amiuopyrene-5.8disu1phonic acid and 3-amin0- 1pyrene-ii.IO-disulphom'c acid l-amino-3-carboethoxyaminoenzene.

1-amino-4-hydroxybenzene-3-carboxylic acid-5-sulphonic acid 1- l-aminobenzenelfi-disulphonic acid 1-amino-3-ethoxybenzenel-arninobenzene-2-carboxylic acid-5-su1phonic acid l-amino zl-amino-thydroxybenzeue-S-carboxylic acid-fi-sulphonic acid 1- 6methy1-2-(3-sulpho-4-aminophenyl)-benzthiazole-sulphonic acid- Condensing agent Shade on cotton 2.4.5.6-tetrachloropyrimidine Yellow.

5-bromo-2.4-6trichloropyrimidine Do.

2.4.5.fi-tetrachloropyrimidine Do.

5-brom0-2.4.6-trichloropyrimidine Do.

2.4.5.G-tetrachloropyrimidine Do.

do Do.

do Do.

do Do.

do Do.

.do Do.

do Yellow-orange.

do Do.

1 7 TABIiE VII 1 8 N 0. Amino disazo dyestufi Condensing agent Shade on cotton 1- HO3S-ON= Q-N=N-ONH2 2.4.5.6-tetrachloropyrimidine Yellow-orange.

3H I IH C 0 CH3 2- HOaSQ-N N =N NH; 2.4.5.6-tetrachloropyrimidine Yellow-orange.

S 0311 CH3 3- N=N-9N: GNH, -bromo-2.4.6-trichloropyrimidine- Yellow-orange.

03H NH O 0 CH3 S 0 H 4- QN=NQ =NNH1 2.4.5.6-tetrach1oropyrimidine Yellow-orange.

O aH 0 Ha CH3 s- HOaS--N=N- N=NONH 2.4.6.6-tetrach1oropyrimidine Orange.

S 03H 6. HO--N=N8 =NONH; 2.4.5.6-tetrachropyrimidine Crange.

S 0 H 0 0 H 1- -N=N N= QNH, 5-bromo-2.4.6-trich1oropyrimidine Orange.

CH3 CH 03H 8 HOaSON=NQ- =NONH; 5-bromo-2.4.fi-trichloropyrimidine- Yellow-orange.

9- N =N -N=NQNH 2.4.5.6-tetrachloropyrimidine Orange.

0 H s 0311 I 10 =NQN=NQNH 5-bromo-2.4.6-trich1oropyrimidine Orange.

SOaH- CH3 NHCOCH;

11- N=NQN=NONH1 2.4.5.6-tetrachloropyrimidine Orange.

SOaH- NHCOOCHa Example 8 65 water and 34.0 parts of sodium bicarbonate. On comple- The condensation product 'from 18.8 parts of 1.3-diaminobenzene-4-sulphonic acid and 262 parts of 2.4.5.6 tetrachloropyrimidine obtained according to Example 3 is dissolved in 300 parts of water and diazotised with parts of hydrochloric acid and 6.9 parts of'sodium nitrite at 0. The diazonium compound formed is then poured into a solution of the condensation product from 31.9 parts of 1-amino-8-hydroxynaphthalene-3.6-disu1- phonic acid and 26.2 parts of 2.4.5.6-tetrachloropyrimidine, obtained according to Example 2, in 200 parts of tion of the coupling, the new dyestufl? of the formula wherein R is the 4.5.6-trich1oropyrimidyl-(2) or the 2.5.6-

1 9 chloride. It is filtered off and dried in the vacuum at 40- 45. It is a dark red powder which dissolves in water with a red colour.

If cotton is treated with a 1% aqueous solution of this (4) naphthalene-azo-naphthalene;

(5) benzene-azo-benzene, (B) copper complexes of the unmetallized monoazo dyestuli grouping; (C) a disazo dyestufl grouping bearing dyestuff at 20 in the foulard, dried and then treated with 5 from 2 to 4 HO S-groups and selected from the group a 2% sodium carbonate solution which contains 30% consisting of sodium chloride, steamed for 5 minutes at 100-103", then (1) benzene-azo-benzene-azo-benzene, rinsed and soaped for 30 minutes at the boil, then a blue- (2) benzene-azo-benzene-azo-naphthalene, ish red dyeing is obtained which is fast to boiling. 3) benzene-azo-naphthalene-azo-benzene.

Dyestuffs having similar properties are obtained if in- 10 2. A monoazo dyestuif of the formula stead of the diazo components obtained by condensation X of 1.3-diaminobenzene-4-sulphonic acid with 2.4.5 .6-tetra- I chloropyrimidine the corresponding number of parts of p the drazo components named in the followmg Table VIII are used, and instead of the coupling component obtained 5 Y by condensation of 1-amino-8-hydroxynaphthalene-3.6-disulphonic acid and 2.4.5.6-tetrachloropyrimidine, the corwherein A is a sulphonated benzene radical, X represents responding number of parts of the coupling components a member selected from the group conslstrng of hydrogen listed in the same table are used. and lower alkyl, Y represents a member selected from the TABLE VIII Diazonium compound from No. Coupling component Condensing agent Shagte on OH Diaminobenzene compound Condensation agent 1 1.3-diaminobenzene-4-sul- -bromo-2.4.G-trichloropyrirnl-amino-S-hydroxynaphtha- 5-bromo-2.4.6-trich1oropy- Blueish phonic acid. ine. lene-Bfirdisulphonic acid. rimidine. red. do .do 1-amino-B-hydroxynaphthado D0.

. lone-4.6-disulphonic acid. -..do 2.4.5.6-tetrachloropyrimidine .do 2.4.5.6-tetrachloropyrimidme D0.

1.4-diaminobenzene-3-suldo do do Violet.

phonic acid. .d0 5-bromo-2.4.6-trichloropyrimdo B-bromo-ZA.G-trichloropyrim- D0.

idine. idine. 6 d0 .d0 1-amino-8-hydroxynaphtha- ,do D0- lene-3.6disulphonie acid. 7 d0 2.4.5.6-tetraehloropyrimidine. do 2.4.5.6-tetrachloropyrimidine. D0

1.3;diaminobenzene-4-su1- do do 5-bromo-2A.6-triohl0r0pyriur Bluelsh phonic acid. idine. I red. do 5-i2tj1mo-2.4.6-trichloropyrirndo 2.4.5.6-tetrachloropyrimid1ne.. D0-

Example 9 Cotton or staple fibre is printed by the usual methods with the following printing paste:

After drying, the goods are steamed for 10-15 minutes or the print is fixed for 5 minutes at 145150, whereupon they are rinsed well and soaped for minutes at the boil. The pure red print has excellent wet fastness properties.

The printing colour described above stores well.

What we claim is:

1. Water-soluble organic dyestuff consisting essentially of (I) from one to two trichloropyrimidyl residues of 2,4,5,6-tetrachloropyrimidine, (II) a dyestuff grouping of which one exchangeable hydrogen atom is replaced for each trichloropyrimidyl residue and (III) a divalent bridge member, NI-I- for each trichloropyrimidyl residue, each of said bridge members being connected with one of its valences to a trichloropyrimidyl residue (I) in replacement of one of the four chlorine atoms of the 2,4,5,6- tetrachloropyrimidine and With its other valence to the site of a replaced exchangeable hydrogen atom of (II); the dyestuif grouping being a member selected from the group consisting of (A) an unmetallized monoazo dyestuff grouping hearing at most 4 HO S-groups and selected from the group consisting of 1) benzene-azo-naphthalene,

(2) diphenyl-azo-naphthalene,

(3) benzene-azo-S-pyrazolone,

group consisting of hydrogen, lower alkyl, lower alkoxy,

lower acylamino and lower alkoxycarbonylamino groups,

and Py represents a pyrimidyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 C-halogen atoms in the o-position and l C-halogen atom in the In-position to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80.

3. A monazo dyestuff of the formula wherein A'N=N is a radical of a diazo component of the benzene series, B represents the radical of a middle component of the naphthalene series, Py represents a pyrimidyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 C-halogen atoms in the o-position and 1 C-halogen atom in the mposition to a ring nitrogen atom, the halogen having an wherein A--N=N- is a radical of a diazo component of the naphthalene series, B represents the radical of a middle component of the benzene series, Py represents a 7 21 pyrimidyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 C-halogen atoms in the o-position and 1 C-halogen atom in the mposition to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80, Z represents a member selected from the group consisting of OH and NH bound in o-position to the azo group, p represents a whole positive number of at most 2, and q represents a whole positive number of at most 4, the SO H and NH-Py groups being directly bound to one of the radicals A and B.

5. A monoazo dyestuff of the formula wherein AN=N- is a radical of a diazo component of the pyrazole series, B represents the radical of a middle component of the benzene series, Py represents a pyrimidyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 C-halogen atoms in the o-position and 1 Clhalogen atom in the mposition to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80, Z represents a member selected from the group consisting of OH and NH bound in o-position to the azo group, p represents a whole positive number of at most 2, and q represents a whole positive number of at most 4, the SO H and -NHPy groups being directly bound to one of the radicals A and B.

6. A monoazo dyestufi of the formula wherein AN=N- is a radical of a diazo component of the benzene series, B represents the radical of a middle component of the pyrazole series, Py represents a pyrimidyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 C-halogen atoms in the o-position and 1 C-halogen atom in the m-position to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80, Z represents a member selected from the group consisting of OH and NH bound in o-position to the azo group, p represents a whole positive number of at most 2, and q represents a whole positive number of at most 4, the SO H and NH-Py groups being directly bound to one of the radicals A and B. Y

7. A disazo dyestufi of the formula wherein A represents a sulphonated naphthalene radical, B is the radical of a middle component of the benzene series, X represents a member selected from the group consisting of hydrogen and lower alkyl, Y represents a member selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, lower acylamino and lower alkoxycarbonylamino groups and Py represents a py rirnidyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 C-halogen atoms in the o-position and 1 C-halogen atom in the m-position to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80.

8. A disazo dyestuff of the formula 22 4 wherein A represents a sulphonated benzene radical, B is the radical of a middle component of the naphthalene series, X represents a member selected from the group consisting of hydrogen and lower alkyl, Y represents a member selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, lower acylamino and lower alkoxycarbonylamino groups and Py represents a pyrimidyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 C-halogen atoms in the o-position and 1 C-halogen atom in the m-position to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80.

9. A disazo dyestutf of the formula wherein A is a sulphonated benzene radical, B is the radical of a middle component of the benzene series, X represents a member selected from the group consisting of hydrogen and lower alkyl, Y represents a member selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, lower acylamino and lower alkoxycarbonylamino groups and Py represents a pyrimidyl radical bound to the NH group in the o-position to a ring nitrogen atom and containing 2 C-halogen atoms in the o-position and 1 C-halogen atom in the m-position to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80.

4 10. A monoazo dyestuff of the formula wherein A represents a radical of the benzene series, B represents a radical of the naphthalene series, Py represents a pyrimidyl radical bound to the NH group in o-position to a ring nitrogen atom and containing 2 halogen atoms in the o-position and 1 halogen atom in the m-position to a ring nitrogen atom, the halogen having an atomic weight of at least 35 and at most 80, k represents a whole positive number of at most 2 and q represents a whole positive number of at most 4, the group -(CO) OCuO being bound to vicinal positions with respect to the azo group, the SO H and NHPy groups being directly bound to one of the radicals A and B.

11. The monoazo dyestuif of the formula 01 S0311 H0 NHCO N=N NH--O \X a Xr-C 803E H038 SOQH 01 wherein one of X and X is =N- and the other of X and X is CCl 12. The monoazo dyestufr" of the formula NHCOOHa HOaS SOaH wherein one of X and X is =N and the other is 2'3 24 13. The monoazo dyestufi of the formula 15. The cupriferous monoazo dyestuff of the formula so H ('31 Cl N-C H3OC-CN=N 1 I! ll N-C 5 0 011-0 NH-O X2 N 0-011 E NHC X2 X =0 X1=C C1 SO3H C1 S O2CH Hogs SO3H H038 w wherein one of X and X is =N-- and the other of X and X is wherein one of X and X is =N- and the other of X and X is o-c1 15 /C Cl References Cited 14. The cupriferous monoazo dyestufi of the formula UNITED STATES PATENTS so H O C 1,667,312 4/1928 Fntzsche 260153 1 20 1,886,480 11/1932 Haller et a1 260-153 i 01 2,396,659 4/ 1946 Kaiser 260-146 X J; 2,935,506 5/1960 Heslop et a1. 260154 S0311 HO;S NHC X, OTHER REFERENCES X =C Johnson et al., Chemical Reviews, vol. 13, pp. 193- 01 M 303, 1933, pp. 220 and 227-8 relied on.

wherein one of X and X is =N and the other of X CHARLES P'immy Examinerand 2 18 LEON ZITVER, Examiner.

\ R. K. JACKSON, R. J. FINNEGAN,

0-01 Asszstant Examiners. 

1. WATER-SOLUBLE ORGANIC DYESTUFF CONSISTING ESSENTIALLY OF (I) FROM ONE TO TWO TRICHLOROPYRIMIDYL RESIDUES OF 2, 4, 5, 6-TETRACHLOROPYRIMIDINE, (II) A DYESTUFF GROUPING OF WHILE ONE EXCHANGEABLE HYDROGEN ATOM IS REPLACED FOR EACH TRICHLOROPYRIMIDYL RESIDUE AND (III) A DIVALENT BRIDGE MEMBER, -NH- FOR EACH TRICHLOROPYRIMIDYL RESIDUE, EACH OF SAID BRIDGE MEMBERS BEING CONNECTED WITH ONE OF ITS VALENCES TO A TRICHLOROPYRIMIDYL RESIDUE (I) IN REPLACEMENT OF ONE OF THE FOUR CHLORINE ATOMS OF THE 2, 4, 5, 6TETRACHLOROPYRIMIDINE AND WITH ITS OTHER VALENCE TO THE SITE OF A REPLACED EXCHANGEABLE HYDROGEN ATOM OF (II); THE DYESTUFF GROUPING BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OF (A) AN UNMETALLIZED MONOAZO DYESTUFF GROUPING BEARING AT MOST 4 HO3S-GROUPS AND SELECTED FROM THE GROUP CONSISTING OF (1) BENZENE-AZO-NAPHTHALENE, (2) DIPHENYL-AZO-NAPHTHALENE, (3) BENZENE-AZO-5-PYRAZOLONE, (4) NAPHTHALENE-AZO-NAPHTHALENE; (5) BENZENE-AZO-BENZENE, (B) COPPER COMPLEXES OF THE UNMETALLIZED MONOAZO DYESTUFF GROUPING; (C) A DISAZO DYESTUFF GROUPING BEARING FROM 2 TO 4 HO3S-GROUPS AND SELECTED FROM THE GROUP CONSISTING OF (1) BENZENE-AZO-BENZENE-AZO-BENZENE. (2) BENZENE-AZO-BENZENE-AZO-NAPHTHALENE, (3) BENZENE-AZO-NAPHTHALENE-AZO-BENZENE. 